US11286227B2 - Processes for preparing 2-isopropenyl-5-methyl-4-hexenoic acid, 2-isopropenyl-5-methyl-4-hexen-1-ol, and a carboxylate ester thereof - Google Patents
Processes for preparing 2-isopropenyl-5-methyl-4-hexenoic acid, 2-isopropenyl-5-methyl-4-hexen-1-ol, and a carboxylate ester thereof Download PDFInfo
- Publication number
- US11286227B2 US11286227B2 US17/234,872 US202117234872A US11286227B2 US 11286227 B2 US11286227 B2 US 11286227B2 US 202117234872 A US202117234872 A US 202117234872A US 11286227 B2 US11286227 B2 US 11286227B2
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- US
- United States
- Prior art keywords
- methyl
- isopropenyl
- hexen
- mol
- group
- Prior art date
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- NNVQOMNUZSZZAL-UHFFFAOYSA-N 5-methyl-2-prop-1-en-2-ylhex-4-enoic acid Chemical compound CC(C)=CCC(C(C)=C)C(O)=O NNVQOMNUZSZZAL-UHFFFAOYSA-N 0.000 title claims abstract description 69
- CZVXBFUKBZRMKR-UHFFFAOYSA-N lavandulol Chemical compound CC(C)=CCC(CO)C(C)=C CZVXBFUKBZRMKR-UHFFFAOYSA-N 0.000 title claims description 82
- 238000000034 method Methods 0.000 title claims description 40
- 230000008569 process Effects 0.000 title claims description 16
- -1 carboxylate ester Chemical class 0.000 title description 75
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims abstract description 50
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 39
- FTRINFHMTBCRER-UHFFFAOYSA-N 2-methylbut-3-en-2-yl 3-methylbut-2-enoate Chemical compound CC(C)=CC(=O)OC(C)(C)C=C FTRINFHMTBCRER-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 238000010537 deprotonation reaction Methods 0.000 claims abstract description 15
- 238000006462 rearrangement reaction Methods 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 10
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract 3
- CVYYCNPRYFOPIB-UHFFFAOYSA-N 6-methyl-3-prop-1-en-2-ylhept-5-enoic acid Chemical compound CC(C)=CCC(C(C)=C)CC(O)=O CVYYCNPRYFOPIB-UHFFFAOYSA-N 0.000 claims description 22
- 239000002904 solvent Substances 0.000 description 78
- 239000011541 reaction mixture Substances 0.000 description 71
- 238000006243 chemical reaction Methods 0.000 description 57
- BQSAHKKCRPWRJK-UHFFFAOYSA-N 5-methyl-2-propan-2-ylidenehex-4-enoic acid Chemical compound CC(C)=CCC(=C(C)C)C(O)=O BQSAHKKCRPWRJK-UHFFFAOYSA-N 0.000 description 53
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 45
- 150000002430 hydrocarbons Chemical group 0.000 description 40
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 38
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 37
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 36
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 34
- 238000002360 preparation method Methods 0.000 description 25
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000002585 base Substances 0.000 description 21
- 230000009257 reactivity Effects 0.000 description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 19
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- 238000004821 distillation Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000008346 aqueous phase Substances 0.000 description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 14
- 239000012074 organic phase Substances 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 14
- 230000010933 acylation Effects 0.000 description 13
- 238000005917 acylation reaction Methods 0.000 description 13
- 239000003638 chemical reducing agent Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000006297 dehydration reaction Methods 0.000 description 11
- 229960004132 diethyl ether Drugs 0.000 description 11
- 238000005809 transesterification reaction Methods 0.000 description 11
- YYPNJNDODFVZLE-UHFFFAOYSA-N 3-methylbut-2-enoic acid Chemical compound CC(C)=CC(O)=O YYPNJNDODFVZLE-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 10
- 230000002411 adverse Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 10
- 229910001873 dinitrogen Inorganic materials 0.000 description 10
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 10
- 150000008282 halocarbons Chemical class 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 10
- 229930195734 saturated hydrocarbon Natural products 0.000 description 10
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 10
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000000877 Sex Attractant Substances 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 9
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 9
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 239000004215 Carbon black (E152) Substances 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 241001465977 Coccoidea Species 0.000 description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 150000001735 carboxylic acids Chemical class 0.000 description 8
- 239000004210 ether based solvent Substances 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 238000001819 mass spectrum Methods 0.000 description 8
- 229920006395 saturated elastomer Polymers 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 7
- 239000002168 alkylating agent Substances 0.000 description 7
- 229940100198 alkylating agent Drugs 0.000 description 7
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 238000000605 extraction Methods 0.000 description 7
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 description 7
- 238000010791 quenching Methods 0.000 description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 7
- STLUIDJQVVNOAV-UHFFFAOYSA-N (5-methyl-2-prop-1-en-2-ylhex-4-enyl) 3-methylbut-2-enoate Chemical compound CC(C)=CCC(C(C)=C)COC(=O)C=C(C)C STLUIDJQVVNOAV-UHFFFAOYSA-N 0.000 description 6
- HNVRRHSXBLFLIG-UHFFFAOYSA-N 3-hydroxy-3-methylbut-1-ene Chemical compound CC(C)(O)C=C HNVRRHSXBLFLIG-UHFFFAOYSA-N 0.000 description 6
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- OCWLYWIFNDCWRZ-UHFFFAOYSA-N Methyl (S)-2-Methylbutanoate Chemical compound CCC(C)C(=O)OC OCWLYWIFNDCWRZ-UHFFFAOYSA-N 0.000 description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical class ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- MOIPGXQKZSZOQX-UHFFFAOYSA-N carbonyl bromide Chemical class BrC(Br)=O MOIPGXQKZSZOQX-UHFFFAOYSA-N 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 239000012280 lithium aluminium hydride Substances 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000002734 organomagnesium group Chemical group 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000011780 sodium chloride Substances 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- WBUQEUATHWMFQO-UHFFFAOYSA-N (5-methyl-2-prop-1-en-2-ylhex-4-enyl) 2-methylbutanoate Chemical compound CCC(C)C(=O)OCC(C(C)=C)CC=C(C)C WBUQEUATHWMFQO-UHFFFAOYSA-N 0.000 description 5
- RWJPUYBXEUWGPU-UHFFFAOYSA-N (5-methyl-2-prop-1-en-2-ylhex-4-enyl) methanesulfonate Chemical compound CC(C)=CCC(C(C)=C)COS(C)(=O)=O RWJPUYBXEUWGPU-UHFFFAOYSA-N 0.000 description 5
- NQCUUXYGJVLXAT-UHFFFAOYSA-N (5-methyl-2-prop-1-en-2-ylhex-4-enyl) propanoate Chemical compound CCC(=O)OCC(C(C)=C)CC=C(C)C NQCUUXYGJVLXAT-UHFFFAOYSA-N 0.000 description 5
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 5
- 125000006023 1-pentenyl group Chemical group 0.000 description 5
- 125000006017 1-propenyl group Chemical group 0.000 description 5
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 5
- GLCIPJOIEVLTPR-UHFFFAOYSA-N 2-chlorohexane Chemical compound CCCCC(C)Cl GLCIPJOIEVLTPR-UHFFFAOYSA-N 0.000 description 5
- 125000006029 2-methyl-2-butenyl group Chemical group 0.000 description 5
- 125000006024 2-pentenyl group Chemical group 0.000 description 5
- 0 C=C(C)C(CC=C(C)C)C(=O)O.C=CC(C)(C)OC(=O)C=C(C)C.[1*][Mg]C.[H]N([Si](C)(C)C)[Si](C)(C)C Chemical compound C=C(C)C(CC=C(C)C)C(=O)O.C=CC(C)(C)OC(=O)C=C(C)C.[1*][Mg]C.[H]N([Si](C)(C)C)[Si](C)(C)C 0.000 description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 5
- 239000003759 ester based solvent Substances 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 239000005453 ketone based solvent Substances 0.000 description 5
- HYNGAVZPWWXQIU-UHFFFAOYSA-N lavandulyl acetate Chemical compound CC(C)=CCC(C(C)=C)COC(C)=O HYNGAVZPWWXQIU-UHFFFAOYSA-N 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 150000002825 nitriles Chemical class 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 5
- 239000012312 sodium hydride Substances 0.000 description 5
- 229910000104 sodium hydride Inorganic materials 0.000 description 5
- DWRGZMHZIKHDPK-UHFFFAOYSA-N tert-butyl 5-methyl-2-propan-2-ylidenehex-4-enoate Chemical compound CC(C)=CCC(=C(C)C)C(=O)OC(C)(C)C DWRGZMHZIKHDPK-UHFFFAOYSA-N 0.000 description 5
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 4
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 4
- 229910052987 metal hydride Inorganic materials 0.000 description 4
- 150000004681 metal hydrides Chemical class 0.000 description 4
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 4
- 150000004045 organic chlorine compounds Chemical class 0.000 description 4
- 239000002304 perfume Substances 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- BZAZNULYLRVMSW-UHFFFAOYSA-N 2-Methyl-2-buten-3-ol Natural products CC(C)=C(C)O BZAZNULYLRVMSW-UHFFFAOYSA-N 0.000 description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 3
- OVRKATYHWPCGPZ-UHFFFAOYSA-N 4-methyloxane Chemical compound CC1CCOCC1 OVRKATYHWPCGPZ-UHFFFAOYSA-N 0.000 description 3
- ANCLCXLWDBALHX-UHFFFAOYSA-N 5-methyl-2-propan-2-ylidenehex-4-en-1-ol Chemical compound CC(C)=CCC(CO)=C(C)C ANCLCXLWDBALHX-UHFFFAOYSA-N 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 3
- KOPYVJMYPXLAEI-UHFFFAOYSA-N C=C(C)C(CC=C(C)C)C(=O)O.C=CC(C)(C)OC(=O)C=C(C)C.[H]N([Si](C)(C)C)[Si](C)(C)C.[Li]CCCC Chemical compound C=C(C)C(CC=C(C)C)C(=O)O.C=CC(C)(C)OC(=O)C=C(C)C.[H]N([Si](C)(C)C)[Si](C)(C)C.[Li]CCCC KOPYVJMYPXLAEI-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 3
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 229940092714 benzenesulfonic acid Drugs 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- RJGHQTVXGKYATR-UHFFFAOYSA-L dibutyl(dichloro)stannane Chemical compound CCCC[Sn](Cl)(Cl)CCCC RJGHQTVXGKYATR-UHFFFAOYSA-L 0.000 description 3
- 239000000796 flavoring agent Substances 0.000 description 3
- 235000019634 flavors Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 3
- 229940098779 methanesulfonic acid Drugs 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
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- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 1
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- YKONAQSKYPWBIE-UHFFFAOYSA-M magnesium;hexane;bromide Chemical compound [Mg+2].[Br-].CCCC[CH-]C YKONAQSKYPWBIE-UHFFFAOYSA-M 0.000 description 1
- KKUBUMXTPYYCHL-UHFFFAOYSA-M magnesium;hexane;chloride Chemical compound [Mg+2].[Cl-].CCCC[CH-]C KKUBUMXTPYYCHL-UHFFFAOYSA-M 0.000 description 1
- BVUQKCCKUOSAEV-UHFFFAOYSA-M magnesium;methylbenzene;bromide Chemical compound [Mg+2].[Br-].CC1=CC=[C-]C=C1 BVUQKCCKUOSAEV-UHFFFAOYSA-M 0.000 description 1
- JFWWQYKSQVMLQU-UHFFFAOYSA-M magnesium;pentane;chloride Chemical compound [Mg+2].[Cl-].CCCC[CH2-] JFWWQYKSQVMLQU-UHFFFAOYSA-M 0.000 description 1
- UGVPKMAWLOMPRS-UHFFFAOYSA-M magnesium;propane;bromide Chemical compound [Mg+2].[Br-].CC[CH2-] UGVPKMAWLOMPRS-UHFFFAOYSA-M 0.000 description 1
- IUYHWZFSGMZEOG-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].C[CH-]C IUYHWZFSGMZEOG-UHFFFAOYSA-M 0.000 description 1
- RYEXTBOQKFUPOE-UHFFFAOYSA-M magnesium;propane;chloride Chemical compound [Mg+2].[Cl-].CC[CH2-] RYEXTBOQKFUPOE-UHFFFAOYSA-M 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- MCVVUJPXSBQTRZ-ONEGZZNKSA-N methyl (e)-but-2-enoate Chemical compound COC(=O)\C=C\C MCVVUJPXSBQTRZ-ONEGZZNKSA-N 0.000 description 1
- MBAHGFJTIVZLFB-SNAWJCMRSA-N methyl (e)-pent-2-enoate Chemical compound CC\C=C\C(=O)OC MBAHGFJTIVZLFB-SNAWJCMRSA-N 0.000 description 1
- FZIBCCGGICGWBP-UHFFFAOYSA-N methyl 3-methylbut-2-enoate Chemical compound COC(=O)C=C(C)C FZIBCCGGICGWBP-UHFFFAOYSA-N 0.000 description 1
- 229940102396 methyl bromide Drugs 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- VREBQIQYKKRJRY-UHFFFAOYSA-N pent-2-enoyl bromide Chemical compound C(CC)=CC(=O)Br VREBQIQYKKRJRY-UHFFFAOYSA-N 0.000 description 1
- GHZXBFJJTBWYTH-UHFFFAOYSA-N pent-2-enoyl pent-2-enoate Chemical compound CCC=CC(=O)OC(=O)C=CCC GHZXBFJJTBWYTH-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 1
- RIBFXMJCUYXJDZ-UHFFFAOYSA-N propanoyl bromide Chemical compound CCC(Br)=O RIBFXMJCUYXJDZ-UHFFFAOYSA-N 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012419 sodium bis(2-methoxyethoxy)aluminum hydride Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- ZFDIRQKJPRINOQ-UHFFFAOYSA-N transbutenic acid ethyl ester Natural products CCOC(=O)C=CC ZFDIRQKJPRINOQ-UHFFFAOYSA-N 0.000 description 1
- YJGJRYWNNHUESM-UHFFFAOYSA-J triacetyloxystannyl acetate Chemical compound [Sn+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O YJGJRYWNNHUESM-UHFFFAOYSA-J 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
Definitions
- the present invention relates to processes for preparing 2-isopropenyl-5-methyl-4-hexenoic acid, 2-isopropenyl-5-methyl-4-hexen-1-ol, and a carboxylate ester thereof.
- 2-Isopropenyl-5-methyl-4-hexen-1-ol (generic name: lavandulol) is known as a flavor ingredient of lavender oil and lavandin oil and widely used as a perfume in cosmetics and fragrances.
- Natural essential oils contain an (R)-optical isomer thereof having an herbal citrus flavor. Meanwhile, an (S)-optical isomer thereof has only weak odor. Therefore, a mixture of the optical isomers is chemically synthesized at less costs.
- 2-Isopropenyl-5-methyl-4-hexen-1-yl carboxylate is reported to be a component of sex pheromone of mealybugs, for example, vine mealybug (scientific name: Planococcus ficus ) (Non-Patent Literature 1 listed below), banana mealybug (scientific name: Dysmicoccus grassii ) (Non-Patent Literature 2 listed below), pink hibiscus mealybug (scientific name: Maconelhcoccus hirsutus ) (Non-Patent Literature 3 listed below), and Madeira mealybug (scientific name: Phenacoccus madeirensis ) (Non-Patent Literature 4 listed below).
- 2-Isopropenyl-5-methyl-4-hexenoic acid is a useful precursor of for 2-isopropenyl-5-methyl-4-hexen-1-ol. Reduction of a carboxyl moiety of this precursor into an alcohol moiety with a reducing agent easily gives 2-isopropenyl-5-methyl-4-hexen-1-ol.
- 2-isopropenyl-5-methyl-4-hexenoic acid is known to easily undergo positional isomerization of the carbon-carbon double bond between the ⁇ - and ⁇ -positions into the carbonyl-conjugated double bond between the ⁇ - and ⁇ -positions in a basic condition.
- This positional isomerization results in by-production of 2-isopropylidene-5-methyl-4-hexenoic acid, which is a regioisomer of 2-isopropenyl-5-methyl-4-hexenoic acid. It is difficult to separate this regioisomer industrially. Then, when the carboxyl moiety of 2-isopropenyl-5-methyl-4-hexenoic acid is reduced, the carboxyl moiety of 2-isopropylidene-5-methyl-4-hexenoic acid is also reduced at the same time.
- This intermixed 2-isopropylidene-5-methyl-4-hexen-1-ol may cause an influence to the native flavor of 2-isopropenyl-5-methyl-4-hexen-1-ol used as a perfume, and also an adverse effect of inhibiting the function of 2-isopropenyl-5-methyl-4-hexen-1-yl carboxylate as a sex pheromone component of mealybugs. Therefore, contamination with the regioisomer is required to be minimized.
- a process for preparing 2-isopropenyl-5-methyl-4-hexenoic acid is known wherein 2-methyl-3-buten-2-yl 3-methyl-2-butenoate is converted into its dienolate using a base and then the dienolate is subjected to a rearrangement reaction.
- Sodium hydride is used as a base, as reported in the following Patent Literature 1 and Non-Patent Literature 5.
- Lithium bis(trimethylsilyl)amide is used as a base, as reported in the following Patent Literature 1.
- Patent Literature 1 and Non-Patent Literature 5 in which sodium hydride is used as a base, generate a large amount of a by-product, 2-isopropylidene-5-methyl-4-hexenoic acid, which is a regioisomer of 2-isopropenyl-5-methyl-4-hexenoic acid.
- the method described in Patent Literature 1, in which lithium bis(trimethylsilyl)amide is used as a base requires the reaction to be carried out in a ultralow temperature. If the method is carried out in an industrially practical reaction temperature, a conversion is low to give a low yield, and the regioisomer is by-produced.
- the prior technologies fail to offer any industrial and economical, large-scale preparation of the envisaged compound.
- the present invention has been made in these circumstances, and aims to overcome the aforesaid problems of the prior art to provide processes for industrially and economically preparing 2-isopropenyl-5-methyl-4-hexenoic acid, 2-isopropenyl-5-methyl-4-hexen-1-ol, and a carboxylate ester thereof, that is, 2-isopropenyl-5-methyl-4-hexen-1-yl carboxylate.
- the present inventors have found that 2-isopropenyl-5-methyl-4-hexenoic acid is prepared in a favorable yield and quality in industrially practical reaction conditions while suppressing or eliminating decrease in a conversion and by-production of its regioisomer, by subjecting a predetermined Grignard reagent and 1,1,1,3,3,3-hexamethyldisilazane to a deprotonation reaction to form a 1,1,1,3,3,3-hexamethyldisilazane derivative and subjecting 2-methyl-3-buten-2-yl 3-methyl-2-butenoate to a rearrangement reaction in the presence of the 1,1,1,3,3,3-hexamethyldisilazane derivative.
- the present invention has been invented.
- the present inventors have also found that 2-isopropenyl-5-methyl-4-hexenoic acid thus obtained may be used to efficiently and industrially prepare 2-isopropenyl-5-methyl-4-hexen-1-ol and a 2-isopropenyl-5-methyl-4-hexen-1-yl carboxylate, and thus have completed the present invention.
- One aspect of the present invention provides a process for preparing 2-isopropenyl-5-methyl-4-hexenoic acid of the following formula (4):
- R 1 MgX R 1 MgX (1) wherein R 1 represents a linear, branched, or aromatic monovalent hydrocarbon group having 1 to 8 carbon atoms, and X represents a chlorine atom, a bromine atom, or an iodine atom, and 1,1,1,3,3,3-hexamethyldisilazane to a deprotonation reaction to form a 1,1,1,3,3,3-hexamethyldisilazane derivative; and
- Another aspect of the present invention provides a process for preparing 2-isopropenyl-5-methyl-4-hexen-1-ol of the following formula (5):
- Another aspect of the present invention further provides a process for preparing a 2-isopropenyl-5-methyl-4-hexen-1-yl carboxylate of the following general formula (6):
- R 2 represents a linear or branched monovalent hydrocarbon group having 1 to 6 carbon atoms, the process comprising esterifying 2-isopropenyl-5-methyl-4-hexen-1-ol (5) thus prepared to form 2-isopropenyl-5-methyl-4-hexen-1-yl carboxylate (6).
- the present invention makes it possible to efficiently prepare 2-isopropenyl-5-methyl-4-hexenoic acid in high purity in industrially practical reaction conditions without decrease in a conversion and/or by-production of a regioisomer.
- the present invention also makes it possible to industrially and economically prepare 2-isopropenyl-5-methyl-4-hexen-1-ol, which is known as a perfume, and a 2-isopropenyl-5-methyl-4-hexen-1-yl carboxylate, which is a sex pheromone of mealybugs, starting from 2-isopropenyl-5-methyl-4-hexenoic acid.
- Grignard reagent (1) a Grignard reagent of the following general formula (1) (hereinafter referred to also as “Grignard reagent (1)”) and 1,1,1,3,3,3-hexamethyldisilazane to a deprotonation reaction to form a 1,1,1,3,3,3-hexamethyldisilazane derivative (2) will be described below.
- R 1 in the general formula (1) represents a linear, branched, or aromatic monovalent hydrocarbon group having 1 to 8, preferably 1 to 3 carbon atoms.
- Examples of the monovalent hydrocarbon group, R 1 include linear monovalent hydrocarbon groups such as a methyl group, an ethyl group, a 1-propyl group, and a 1-pentyl group; branched monovalent hydrocarbon groups such as a 2-propyl group, a 2-butyl group, a 2-hexyl group, a 2-methylbutyl group, and a 1,1-dimethylethyl group; and aromatic monovalent hydrocarbon groups such as a phenyl group and a p-tolyl group.
- X in the general formula (1) represents a chlorine atom, a bromine atom, or an iodine atom, preferably a chlorine atom.
- Grignard reagent (1) examples include an organomagnesium chloride, an organomagnesium bromide, and an organomagnesium iodide.
- organomagnesium chloride examples include linear organomagnesium chlorides such as methylmagnesium chloride, ethylmagnesium chloride, 1-propylmagnesium chloride, and 1-pentylmagnesium chloride; branched organomagnesium chlorides such as 2-propylmagnesium chloride, 2-butylmagnesium chloride, 2-hexylmagnesium chloride, 2-methylbutylmagnesium chloride, and 1,1-dimethylethylmagnesium chloride; and aromatic organomagnesium chlorides such as phenylmagnesium chloride and p-tolylmagnesium chloride.
- linear organomagnesium chlorides such as methylmagnesium chloride, ethylmagnesium chloride, 1-propylmagnesium chloride, and 1-pentylmagnesium chloride
- branched organomagnesium chlorides such as 2-propylmagnesium chloride, 2-butylmagnesium chloride, 2-hexy
- organomagnesium bromide examples include linear organomagnesium bromides such as methylmagnesium bromide, ethylmagnesium bromide, 1-propylmagnesium bromide, and 1-pentylmagnesium bromide; branched organomagnesium bromides such as 2-propylmagnesium bromide, 2-butylmagnesium bromide, 2-hexylmagnesium bromide, 2-methylbutylmagnesium bromide, and 1,1-dimethylethylmagnesium bromide; and aromatic organomagnesium bromides such as phenylmagnesium bromide and p-tolylmagnesium bromide.
- linear organomagnesium bromides such as methylmagnesium bromide, ethylmagnesium bromide, 1-propylmagnesium bromide, and 1-pentylmagnesium bromide
- branched organomagnesium bromides such as 2-propy
- organomagnesium iodide examples include linear organomagnesium iodides such as methylmagnesium iodide, ethylmagnesium iodide, 1-propylmagnesium iodide, and 1-pentylmagnesium iodide; branched organomagnesium iodides such as 2-propylmagnesium iodide, 2-butylmagnesium iodide, 2-hexylmagnesium iodide, 2-methylbutylmagnesium iodide, and 1,1-dimethylethylmagnesium iodide; and aromatic organomagnesium iodides such as phenylmagnesium iodide and p-tolylmagnesium iodide.
- linear organomagnesium iodides such as methylmagnesium iodide, ethylmagnesium iodide, 1-propylmag
- the Grignard reagent (1) may be used alone or in combination thereof, if necessary.
- the Grignard reagent (1) may be a commercially available one or may be prepared by reacting an organohalide with metal magnesium in a solvent in any known method.
- organohalide examples include organochlorides, organobromides, and organoiodides.
- organochlorides examples include linear organochlorides such as methyl chloride, ethyl chloride, 1-propyl chloride, and 1-pentyl chloride; branched organochlorides such as 2-propyl chloride, 2-butyl chloride, 2-hexyl chloride, 2-methylbutyl chloride, and 1,1-dimethylethyl chloride; and aromatic organochlorides such as phenyl chloride and p-tolyl chloride.
- linear organochlorides such as methyl chloride, ethyl chloride, 1-propyl chloride, and 1-pentyl chloride
- branched organochlorides such as 2-propyl chloride, 2-butyl chloride, 2-hexyl chloride, 2-methylbutyl chloride, and 1,1-dimethylethyl chloride
- aromatic organochlorides such as phenyl chloride and p-tolyl chloride.
- organobromides examples include linear organobromides such as methyl bromide, ethyl bromide, 1-propyl bromide, and 1-pentyl bromide; branched organobromides such as 2-propyl bromide, 2-butyl bromide, 2-hexyl bromide, 2-methylbutyl bromide, and 1,1-dimethylethyl bromide; and aromatic organobromides such as phenyl bromide and p-tolyl bromide.
- linear organobromides such as methyl bromide, ethyl bromide, 1-propyl bromide, and 1-pentyl bromide
- branched organobromides such as 2-propyl bromide, 2-butyl bromide, 2-hexyl bromide, 2-methylbutyl bromide, and 1,1-dimethylethyl bromide
- aromatic organobromides such as phenyl bromide and
- organoiodides examples include linear organoiodides such as methyl iodide, ethyl iodide, 1-propyl iodide, and 1-pentyl iodide; branched organoiodides such as 2-propyl iodide, 2-butyl iodide, 2-hexyl iodide, 2-methylbutyl iodide, and 1,1-dimethylethyl iodide; and aromatic organoiodides such as phenyl iodide and p-tolyl iodide.
- linear organoiodides such as methyl iodide, ethyl iodide, 1-propyl iodide, and 1-pentyl iodide
- branched organoiodides such as 2-propyl iodide, 2-butyl iodide, 2-hexyl iodide
- a solvent to be used in the preparation of Grignard reagent (1) is typically ether solvents such as diethyl ether, methyl t-butyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, and 4-methyltetrahydropyran.
- ether solvents such as diethyl ether, methyl t-butyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, and 4-methyltetrahydropyran.
- the solvent may be used alone or in combination thereof, if necessary.
- the solvent may be used for adjusting a concentration and/or a reaction temperature insofar as it does not adversely affect the preparation of Grignard reagent (1).
- the solvent may be commercially available one.
- An amount of the solvent is preferably from 50 g to 1,000 g, more preferably from 100 g to 500 g, per mol of the organohalide in view of the economy and reactivity.
- a reaction temperature in the preparation of the Grignard reagent (1) is preferably from 20° C. to 120° C., more preferably from 40° C. to 80° C. in view of the reactivity and easy control of a reaction rate.
- An amount of the metal magnesium to be used in the preparation of the Grignard reagent (1) may be set arbitrarily.
- the metal magnesium is used in an excessive amount relative to the organohalide.
- the organohalide has a low boiling point, the organohalide is used in an excessive amount relative to the metal magnesium, and the excess organohalide may be removed in a gaseous form or distilled off in a liquid form.
- 1,1,1,3,3,3-Hexamethyldisilazane is known also as bis(trimethylsilyl)amine.
- the deprotonation reaction may be carried out in the presence of a solvent and, if necessary, under heating or cooling.
- 1,1,1,3,3,3-Hexamethyldisilazane may be a commercially available one or may be prepared in a known reaction of trimethylsilyl chloride with ammonia.
- An amount of 1,1,1,3,3,3-hexamethyldisilazane to be used is preferably from 1.0 to 2.0 mol, more preferably from 1.05 to 1.25 mol, per mol of the Grignard reagent (1), in view of the reactivity and suppression of formation of impurities.
- Examples of the solvent used in the deprotonation reaction include ether solvents such as diethyl ether, methyl t-butyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, and 4-methyltetrahydropyran; and hydrocarbon solvents such as pentane, hexane, heptane, cyclohexane, benzene, and toluene. In view of the reactivity or yield, tetrahydrofuran and diethyl ether are preferred.
- the solvent used in the preparation of the Grignard reagent (1) may be used as such in the deprotonation reaction.
- the solvent to be used in the deprotonation reaction may be alone or in combination thereof, if necessary.
- the solvent may be commercially available one.
- An amount of the solvent is preferably from 100 g to 1,000 g, more preferably from 250 g to 600 g, per mol of the Grignard reagent (1) in view of the reactivity and economy.
- a reaction temperature of the deprotonation reaction is preferably from 0° C. to 120° C., more preferably from 20° C. to 50° C. in view of the reactivity and yield.
- 1,1,1,3,3,3-hexamethyldisilazane derivative is formed in the deprotonation reaction of 1,1,1,3,3,3-hexamethyldisilazane with the Grignard reagent (1).
- the 1,1,1,3,3,3-hexamethyldisilazane derivative (2) thus prepared is theoretically presumed to be a halomagnesium bis(trimethylsilyl)amide of the following general formula (2A):
- X represents a chlorine atom, a bromine atom, or an iodine atom.
- the reaction mixture after the deprotonation reaction may be used as such without being purified, as a base in the subsequent step (i.e., rearrangement reaction).
- spectral data of the 1,1,1,3,3,3-hexamethyldisilazane derivative (2) produced in the deprotonation reaction are not particularly shown.
- 2-Methyl-3-buten-2-yl 3-methyl-2-butenoate (3) may be prepared in any known method. Specifically, examples of the known preparation methods are described in Non-Patent Literature 5, where 2-methyl-3-buten-2-ol is reacted with sodium hydride to form a sodium alkoxide which is then reacted with 3-methyl-2-butenoyl chloride. Alternatively, as described in the present Example, 3-methyl-2-butenoic acid is reacted with 2-methyl-3-buten-2-ol and p-toluenesulfonyl chloride or benzenesulfonyl chloride in the presence of pyridine.
- the rearrangement reaction proceeds by reacting 2-methyl-3-buten-2-yl 3-methyl-2-butenoate (3) with the 1,1,1,3,3,3-hexamethyldisilazane derivative (2) as a base to form a dienolate.
- This rearrangement reaction may be carried out under heating or cooling, if necessary.
- An amount of the 1,1,1,3,3,3-hexamethyldisilazane derivative (2) to be used is preferably from 1.05 mol to 1.5 mol, more preferably from 1.1 to 1.3 mol, per mol of 2-methyl-3-buten-2-yl 3-methyl-2-butenoate (3) in view of the reactivity and suppression of formation of impurities.
- the solvent used in the rearrangement reaction is not particularly limited insofar as it does not adversely affect the reaction.
- Example of the solvent include ether solvents such as diethyl ether, methyl t-butyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, 1,4-dioxane, and 4-methyltetrahydropyran; and hydrocarbon solvents such as pentane, hexane, heptane, cyclohexane, benzene, and toluene.
- tetrahydrofuran and diethyl ether are preferred.
- the solvent used in the preparation of the Grignard reagent or the deprotonation reaction may be used as such.
- a solvent may be used alone or in combination thereof, if necessary.
- the solvent may be commercially available one.
- An amount of the solvent used is preferably from 100 g to 1,000 g, more preferably from 300 g to 700 g, per mol of the 2-methyl-3-buten-2-yl 3-methyl-2-butenoate (3), in view of the reactivity and economy.
- a reaction temperature in the rearrangement reaction is preferably from 25° C. to 80° C., more preferably from 30° C. to 60° C. in view of the reactivity and yield.
- 2-Isopropenyl-5-methyl-4-hexenoic acid (4) may be isolated and purified in any purification method used in ordinary organic syntheses, such as distillation at a reduced pressure and/or various chromatography. In view of the industrial economy, distillation at a reduced pressure is preferred. When a target chemical compound has a sufficient purity, a crude product may be used as such without being purified, in a subsequent step.
- Examples of 2-isopropenyl-5-methyl-4-hexenoic acid (4) obtained in the rearrangement reaction include (R)-2-isopropenyl-5-methyl-4-hexenoic acid, (S)-2-isopropenyl-5-methyl-4-hexenoic acid, and a racemate and a scalemic mixture thereof.
- the reduction reaction may be carried out with a reducing agent and, if necessary, under heating or cooling.
- the reducing agent is not particularly limited and may be any known reducing agent.
- Examples of the reducing agent include hydrogen; boron compounds such as a borane, an alkylborane, a dialkylborane, and a bis(3-methyl-2-butyl)borane; metal hydrides such as a dialkylsilane, a trialkylsilane, an aluminum hydride, an alkylaluminum hydride, a dialkylaluminum hydride, sodium hydride, lithium hydride, potassium hydride, and calcium hydride; and metal hydride complexes such as sodium borohydride, lithium borohydride, potassium borohydride, sodium trimethoxyborohydride, lithium triethylborohydride, sodium aluminum hydride, lithium aluminum hydride, lithium trimethoxyaluminum hydride, lithium diethoxyaluminum hydride, lithium tri-t-butoxyaluminum hydride, and sodium bis(2-methoxyethoxy)aluminum hydride.
- the reducing agent may be used alone or in combination thereof, if necessary.
- the reducing agent may be commercially available one.
- the reduction reaction may be carried out otherwise after converting 2-isopropenyl-5-methyl-4-hexenoic acid (4) into an ester, an acid halide, an acid anhydride, or a mixed acid anhydride.
- An amount of the reducing agent used in the reduction reaction may be set, depending on the reactivity of the reducing agent and/or the reaction mechanism, and is preferably from 0.2 mol to 10.0 mol, more preferably from 0.25 mol to 5.0 mol, per mol of 2-isopropenyl-5-methyl-4-hexenoic acid (4) in view of the reactivity and economy.
- an amount of lithium aluminum hydride is preferably from 0.75 mol to 3.0 mol, more preferably from 1.0 mol to 2.0 mol, per mol of 2-isopropenyl-5-methyl-4-hexenoic acid (4).
- An amount of hydrogen atoms or hydride ions of the reducing agent is preferably from 0.2 mol to 40.0 mol, more preferably from 0.25 mol to 20.0 mol in view of the reactivity and economy.
- An amount of the hydrogen atoms or hydride ions used is decided by the kind of the reducing agent used and/or the amount thereof.
- a solvent used in the reduction reaction is not particularly limited insofar as it does not adversely affect the reaction.
- the solvent examples include water; hydrocarbon solvents such as hexane, heptane, octane, benzene, toluene, and xylene; ether solvents such as diethyl ether, dibutyl ether, cyclopentyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, and 1,4-dioxane; alcohol solvents such as methanol, ethanol, 1-propanol, and 2-propanol; nitrile solvents such as acetonitrile; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as methyl acetate, ethyl acetate, and n-butyl acetate; and aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and
- the solvent may be used alone or in combination thereof, if necessary.
- the solvent may be commercially available one.
- the solvent is preferably an ether solvent such as tetrahydrofuran, diethylene glycol diethyl ether, or 1,4-dioxane.
- ether solvent such as tetrahydrofuran, diethylene glycol diethyl ether, or 1,4-dioxane.
- hydrocarbon solvent such as hexane, heptane, octane, benzene, toluene, or xylene may be also used.
- a reaction temperature in the reduction reaction may be in a temperature range that does not adversely affect the reaction, and is preferably from ⁇ 50° C. to 50° C., more preferably from ⁇ 25° C. to 25° C., in view of a yield and suppression of formation of by-products.
- the reaction temperature is preferably from ⁇ 10° C. to 35° C., more preferably from 0° C. to 30° C.
- the obtained 2-isopropenyl-5-methyl-4-hexen-1-ol (5) may be isolated and purified in any purification method used in ordinary organic synthesis, such as distillation at a reduced pressure and/or various chromatography. In view of the industrial economy, distillation at a reduced pressure is preferred. When the target chemical compound has a sufficient purity, the crude product may be used as such without being purified, in a subsequent step.
- Examples of the 2-isopropenyl-5-methyl-4-hexen-1-ol (5) obtained in the reduction reaction include (R)-2-isopropenyl-5-methyl-4-hexen-1-ol, (S)-2-isopropenyl-5-methyl-4-hexen-1-ol, and a racemate and a scalemic mixture thereof.
- the aforesaid esterification step may be done in any known esterification method, such as (A) an acylation with an acylating agent, (B) a dehydration with a carboxylic acid, (C) a transesterification with a carboxylate ester, and (D) conversion of 2-isopropenyl-5-methyl-4-hexen-1-ol (5) into an alkylating agent, followed by acyloxylation with a carboxylic acid, but not limited to these.
- the aforesaid (A) to (D) will be explained below in detail.
- acylation of 2-isopropenyl-5-methyl-4-hexen-1-ol (5) with an acylating agent may be carried out typically in the presence of a base or catalyst.
- the acylating agent is represented by R 2 COCl, R 2 COBr, or R 2 COOCOR 2 , wherein R 2 represents a linear or branched monovalent hydrocarbon group having 1 to 6 carbon atoms.
- R 2 examples include linear saturated hydrocarbon groups such as a methyl group, an ethyl group, a 1-propyl group, and a 1-butyl group; branched saturated hydrocarbon groups such as a 2-propyl group, a 2-methylpropyl group, a 2-butyl group, a 2-pentyl group, and a 1,1-dimethylethyl group; linear unsaturated hydrocarbon groups such as a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, and a 2-pentenyl group; and branched unsaturated hydrocarbon groups such as a 1-methylpropenyl group, a 2-methylpropenyl group, a 2-methylbutenyl group, and a 2-methyl-2-butenyl group.
- acylating agent examples include carbonyl chlorides, carbonyl bromides, and carboxylic anhydrides.
- Examples of the carbonyl chlorides include linear saturated carbonyl chlorides such as acetyl chloride and propionyl chloride; branched saturated carbonyl chlorides such as 2-methylpropionyl chloride, 2-methylbutanoyl chloride, and 3-methylbutanoyl chloride; linear unsaturated carbonyl chlorides such as 2-butenoyl chloride and 2-pentenoyl chloride; and branched unsaturated carbonyl chlorides such as 2-methyl-2-butenoyl chloride and 3-methyl-2-butenoyl chloride.
- Examples of the carbonyl bromides include linear saturated carbonyl bromides such as acetyl bromide and propionyl bromide; branched saturated carbonyl bromides such as 2-methylpropionyl bromide, 2-methylbutanoyl bromide, and 3-methylbutanoyl bromide; linear unsaturated carbonyl bromides such as 2-butenoyl bromide and 2-pentenoyl bromide; and branched unsaturated carbonyl bromides such as 2-methyl-2-butenoyl bromide and 3-methyl-2-butenoyl bromide.
- linear saturated carbonyl bromides such as acetyl bromide and propionyl bromide
- branched saturated carbonyl bromides such as 2-methylpropionyl bromide, 2-methylbutanoyl bromide, and 3-methylbutanoyl bromide
- linear unsaturated carbonyl bromides such as 2-butenoyl bromide and 2-
- carboxylic anhydrides examples include linear saturated carboxylic anhydrides such as acetic anhydride and propionic anhydride; branched saturated carboxylic anhydrides such as 2-methylpropionic anhydride, 2-methylbutanoic anhydride, and 3-methylbutanoic anhydride; linear unsaturated carboxylic anhydrides such as 2-butenoic anhydride and 2-pentenoic anhydride; and branched unsaturated carboxylic anhydrides such as 2-methyl-2-butenoic anhydride and 3-methyl-2-butenoic anhydride.
- linear saturated carboxylic anhydrides such as acetic anhydride and propionic anhydride
- branched saturated carboxylic anhydrides such as 2-methylpropionic anhydride, 2-methylbutanoic anhydride, and 3-methylbutanoic anhydride
- linear unsaturated carboxylic anhydrides such as 2-butenoic anhydride and 2-pentenoic anhydride
- An amount of the acylating agent used is preferably from 1.0 mol to 30.0 mol, more preferably from 1.0 mol to 5.0 mol, per mol of 2-isopropenyl-5-methyl-4-hexen-1-ol (5) in view of the economy.
- Examples of the base used in the acylation include amines such as triethylamine, pyridine, N,N-dimethylaminopyridine, and N,N-dimethylaniline; organometallic compounds such as n-butyllithium, methyllithium, and phenyllithium; metal hydroxides such as sodium hydroxide and potassium hydroxide; and metal carbonates such as potassium carbonate, sodium carbonate, and sodium bicarbonate.
- amines such as triethylamine, pyridine, N,N-dimethylaminopyridine, and N,N-dimethylaniline
- organometallic compounds such as n-butyllithium, methyllithium, and phenyllithium
- metal hydroxides such as sodium hydroxide and potassium hydroxide
- metal carbonates such as potassium carbonate, sodium carbonate, and sodium bicarbonate.
- An amount of the base used in the acylation is preferably from 1.0 mol to 50.0 mol, more preferably from 1.0 to 10.0 mol per mol of the 2-isopropenyl-5-methyl-4-hexen-1-ol (5) in view of the economy.
- Examples of the catalyst used in the acylation in which the carboxylic anhydride is used as the acylating agent include inorganic acids such as hydrochloric acid, hydrobromic acid, nitric acid, and sulfuric acid; sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid; Lewis acids such as aluminum trichloride, aluminum isopropoxide, zinc chloride, boron trifluoride, boron trichloride, tin tetrachloride, dibutyltin dichloride, titanium tetrachloride, and titanium(IV) isopropoxide; and metallic acetate salts such as sodium acetate and potassium acetate.
- inorganic acids such as hydrochloric acid, hydrobromic acid, nitric acid, and sulfuric acid
- sulfonic acids such as methanesulfonic acid, benzenesulfonic
- An amount of the catalyst used in the acylation is preferably from 0.001 mol to 1.0 mol, more preferably from 0.005 to 0.2 mol, per mol of 2-isopropenyl-5-methyl-4-hexen-1-ol (5) in view of the economy.
- a solvent used in the acylation may be any solvent that does not adversely affect the actions of 2-isopropenyl-5-methyl-4-hexen-1-ol (5), the acylating agent, the base, or the catalyst.
- the solvent examples include halogenated solvents such as methylene chloride and chloroform; hydrocarbon solvents such as hexane, heptane, benzene, and toluene; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and ethylene glycol dimethyl ether; nitrile solvents such as acetonitrile; ketone solvents such as acetone, methyl ethyl ketone, and diisobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; and aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphoric triamide.
- halogenated solvents such as methylene chloride and chloroform
- hydrocarbon solvents such as hexane, heptane,
- the solvent may be used alone or in combination thereof, if necessary.
- the acylation may be carried out without a solvent, depending on an acylating agent to be used.
- the solvent may be commercially available one.
- An amount of the solvent used in the acylation is preferably from 0.0 g to 2,000.0 g, more preferably from 0.0 g to 500.0 g, per mol of 2-isopropenyl-5-methyl-4-hexen-1-ol (5) in view of the economy.
- a reaction temperature in the acylation is preferably from ⁇ 78° C. to 120° C., more preferably from ⁇ 30° C. to 80° C., in view of the reactivity and yield.
- the dehydration reaction of 2-isopropenyl-5-methyl-4-hexen-1-ol (5) with a carboxylic acid may be carried out typically in the presence of an acid or Lewis acid catalyst.
- the carboxylic acid is represented by R 2 —COOH, wherein R 2 is as defined above.
- R 2 examples include linear saturated hydrocarbon groups such as a methyl group, an ethyl group, a 1-propyl group, and a 1-butyl group; branched saturated hydrocarbon groups such as a 2-propyl group, a 2-methylpropyl group, a 2-butyl group, a 2-pentyl group, and a 1,1-dimethylethyl group; linear unsaturated hydrocarbon groups such as a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, and a 2-pentenyl group; and branched unsaturated hydrocarbon groups such as a 1-methylpropenyl group, a 2-methylpropenyl group, a 2-methylbutenyl group, and a 2-methyl-2-butenyl group.
- Examples of the carboxylic acid used in the dehydration reaction include linear saturated carboxylic acids such as acetic acid and propionic acid; branched saturated carboxylic acids such as 2-methylpropionic acid, 2-methylbutanoic acid, and 3-methylbutanoic acid; linear unsaturated carboxylic acids such as 2-butenoic acid and 2-pentenoic acid; and branched unsaturated carboxylic acids such as 2-methyl-2-butenoic acid and 3-methyl-2-butenoic acid.
- Examples of the acid catalyst used in the dehydration reaction include inorganic acids such as hydrochloric acid, hydrobromic acid, nitric acid, and sulfuric acid; and organic acids such as trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid.
- inorganic acids such as hydrochloric acid, hydrobromic acid, nitric acid, and sulfuric acid
- organic acids such as trichloroacetic acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, and p-toluenesulfonic acid.
- the catalyst may be used alone or in combination thereof, if necessary.
- the catalyst may be commercially available one.
- An amount of the catalyst used in the dehydration reaction is preferably from 0.001 to 1.0 mol, more preferably from 0.05 to 0.1 mol, per mol of 2-isopropenyl-5-methyl-4-hexen-1-ol (5) in view of the economy and reactivity.
- the dehydration reaction may be carried out while removing water by-produced in the reaction, for example, by azeotropically distilling off the reaction solvent used and water at normal pressure or at a reduced pressure or by adding a dehydrating agent such as anhydrous magnesium sulfate, a molecular sieve, or dicyclohexylcarbodiimide to the reaction mixture.
- a dehydrating agent such as anhydrous magnesium sulfate, a molecular sieve, or dicyclohexylcarbodiimide
- a solvent used in the dehydration reaction may be any solvent insofar as it does not adversely affect the catalytic activity.
- the solvent examples include halogenated solvents such as methylene chloride and chloroform; hydrocarbon solvents such as hexane, heptane, benzene, and toluene; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and ethylene glycol dimethyl ether; nitrile solvents such as acetonitrile; ketone solvents such as acetone, methyl ethyl ketone, and diisobutyl ketone; and ester solvents such as ethyl acetate and butyl acetate.
- halogenated solvents such as methylene chloride and chloroform
- hydrocarbon solvents such as hexane, heptane, benzene, and toluene
- ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and ethylene glycol
- the solvent may be used alone or in combination thereof, if necessary.
- the solvent may be commercially available one.
- An amount of the solvent used in the dehydration reaction is preferably from 0.0 g to 2000.0 g, more preferably from 0.0 g to 500.0 g, per mol of 2-isopropenyl-5-methyl-4-hexen-1-ol (5), in view of the economy.
- a reaction temperature in the dehydration may be appropriately set, depending on a catalyst to be used.
- the reaction temperature is preferably from ⁇ 30° C. to 200° C., more preferably from 25 to 100° C. in view of the reactivity and yield.
- the reaction temperature is preferably the azeotropic point or above of the solvent and water at normal pressure or at a reduced pressure.
- the transesterification between 2-isopropenyl-5-methyl-4-hexen-1-ol (5) and a carboxylate ester is carried out typically in the presence of a catalyst and can be facilitated by removing an alcohol by-produced from the carboxylate ester, at normal pressure or a reduced pressure.
- the carboxylate ester is represented by R 2 COOR 3 , wherein R 2 is as defined above, and R 3 represents a hydrocarbon group having 1 to 6 carbon atoms.
- R 2 in the carboxylate ester used in the transesterification is linear saturated hydrocarbon groups such as a methyl group, an ethyl group, a 1-propyl group, and a 1-butyl group; branched saturated hydrocarbon groups such as a 2-propyl group, a 2-methylpropyl group, a 2-butyl group, a 2-pentyl group, and a 1,1-dimethylethyl group; linear unsaturated hydrocarbon groups such as a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, and a 2-pentenyl group; and branched unsaturated hydrocarbon groups such as a 1-methylpropenyl group, a 2-methylpropenyl group, a 2-methylbutenyl group, and a 2-methyl-2-butenyl group.
- R 3 in the carboxylate ester examples include a hydrocarbon group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group.
- Specific examples of the carboxylate ester include methyl carboxylate, ethyl carboxylate, propyl carboxylate, butyl carboxylate, and phenyl carboxylate.
- the carboxylate ester is preferably methyl carboxylate or ethyl carboxylate in view of the economy, reactivity, and easy removal of an alcohol by-produced from the carboxylate ester.
- carboxylate ester examples include linear saturated methyl carboxylates such as methyl acetate and methyl propionate; branched saturated methyl carboxylates such as methyl 2-methylpropionate, methyl 2-methylbutanoate, and methyl 3-methylbutanoate; linear unsaturated methyl carboxylates such as methyl 2-butenoate and methyl 2-pentenoate; branched unsaturated methyl carboxylates such as methyl 2-methyl-2-butenoate and methyl 3-methyl-2-butenoate; linear saturated ethyl carboxylates such as ethyl acetate and ethyl propionate; branched saturated ethyl carboxylates such as ethyl 2-methylpropionate, ethyl 2-methylbutanoate, and ethyl 3-methylbutanoate; linear unsaturated ethyl carboxylates such as ethyl 2-butenoate and ethyl 2-pentenoate;
- An amount of the carboxylate ester is preferably from 1.0 to 30.0 mol, more preferably from 1.0 to 5.0 mol, per mol of 2-isopropenyl-5-methyl-4-hexen-1-ol (5).
- Examples of the catalyst used in the transesterification include acids such as hydrochloric acid, sulfuric acid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and Amberlyst 15; alkali metal salts of alcohols, such as sodium methoxide, sodium ethoxide, and potassium t-butoxide; metal carboxylates such as sodium acetate, potassium acetate, calcium acetate, tin acetate, zinc acetate, and aluminum acetate; and Lewis acids such as aluminum trichloride, aluminum ethoxide, aluminum isopropoxide, zinc diisopropoxide, zinc diethoxide, zinc dimethoxide, zinc chloride, boron trifluoride, boron trichloride, tin tetrachloride, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltin
- An amount of the catalyst used in the transesterification is preferably from 0.001 to 1.0 mol, more preferably from 0.005 to 0.1 mol, per mol of 2-isopropenyl-5-methyl-4-hexen-1-ol (5).
- a solvent used in the transesterification may be any solvent insofar as it does not adversely affect the action of the catalyst to be used.
- the solvent examples include halogenated solvents such as methylene chloride and chloroform; hydrocarbon solvents such as hexane, heptane, benzene, and toluene; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and ethylene glycol dimethyl ether; nitrile solvents such as acetonitrile; ketone solvents such as acetone, methyl ethyl ketone, and diisobutyl ketone; and ester solvents such as ethyl acetate and butyl acetate.
- halogenated solvents such as methylene chloride and chloroform
- hydrocarbon solvents such as hexane, heptane, benzene, and toluene
- ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and ethylene glycol
- the solvent may be used alone or in combination thereof, if necessary.
- the transesterification may be carried out without a solvent, only with 2-isopropenyl-5-methyl-4-hexen-1-ol (5), a carboxylate ester, and a catalyst.
- the solvent may be commercially available one.
- An amount of the solvent used in the transesterification is preferably from 0.0 g to 2,000.0 g, more preferably from 0.0 g to 500.0 g, per mol of 2-isopropenyl-5-methyl-4-hexen-1-ol (5) in view of the economy.
- a reaction temperature in the transesterification may be appropriately selected, depending on the kind of a carboxylate ester and a catalyst to be used. Typically, the reaction temperature is preferably from 0° C. to 200° C., more preferably from 50° C. to 160° C. When the reaction is facilitated by removing an alcohol by-produced from the carboxylate ester, the reaction temperature is preferably a boiling point or above of the alcohol to be removed at normal pressure or a reduced pressure.
- the conversion of 2-isopropenyl-5-methyl-4-hexen-1-ol (5) into an alkylating agent, followed by acyloxylation with a carboxylic acid is typically carried out by converting the alcohol compound into its corresponding alkylating agent, followed by a reaction with a carboxylic acid in the presence of a base.
- alkylating agent examples include halides such as chlorides, bromides, and iodides; and sulfonate esters such as methanesulfonate esters, benzenesulfonate esters, and p-toluenesulfonate esters.
- the carboxylic acid is represented by R 2 —COOH, wherein R 2 is as defined above.
- R 2 examples include linear saturated hydrocarbon groups such as a methyl group, an ethyl group, a 1-propyl group, and a 1-butyl group; branched saturated hydrocarbon groups such as a 2-propyl group, a 2-methylpropyl group, a 2-butyl group, a 2-pentyl group, and a 1,1-dimethylethyl group; linear unsaturated hydrocarbon groups such as a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, and a 2-pentenyl group; and branched unsaturated hydrocarbon groups such as a 1-methylpropenyl group, a 2-methylpropenyl group, a 2-methylbutenyl group, and a 2-methyl-2-butenyl group.
- Examples of the carboxylic acid used in the acyloxylation include linear saturated carboxylic acids such as acetic acid and propionic acid; branched saturated carboxylic acids such as 2-methylpropionic acid, 2-methylbutanoic acid, and 3-methylbutanoic acid; linear unsaturated carboxylic acids such as 2-butenoic acid and 2-pentenoic acid; and branched unsaturated carboxylic acids such as 2-methyl-2-butenoic acid and 3-methyl-2-butenoic acid.
- carboxylic acid instead of the carboxylic acid, available metal carboxylate, such as sodium carboxylates and potassium carboxylates, may be used, without using a base.
- metal carboxylate such as sodium carboxylates and potassium carboxylates
- Examples of the base used in the acyloxylation include amines such as triethylamine, pyridine, N,N-dimethylaminopyridine, and dimethylaniline; organometallic compounds such as n-butyllithium, methyllithium, and phenyllithium; metal hydroxides such as sodium hydroxide and potassium hydroxide; metal carbonates such as potassium carbonate, sodium carbonate, and sodium bicarbonate; and metal hydrides such as sodium hydride and potassium hydride.
- amines such as triethylamine, pyridine, N,N-dimethylaminopyridine, and dimethylaniline
- organometallic compounds such as n-butyllithium, methyllithium, and phenyllithium
- metal hydroxides such as sodium hydroxide and potassium hydroxide
- metal carbonates such as potassium carbonate, sodium carbonate, and sodium bicarbonate
- metal hydrides such as sodium hydride and potassium hydride.
- An amount of the base used in the acyloxylation is preferably from 1.0 mol to 50.0 mol, more preferably from 1.0 to 10.0 mol, per mol of 2-isopropenyl-5-methyl-4-hexen-1-ol (5) in view of the economy.
- Any solvent may be used in the acyloxylation insofar as it does not give adverse effect to the reactive species.
- the solvent examples include halogenated solvents such as methylene chloride and chloroform; hydrocarbon solvents such as hexane, heptane, benzene, and toluene; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and ethylene glycol dimethyl ether; nitrile solvents such as acetonitrile; ketone solvents such as acetone, methyl ethyl ketone, and diisobutyl ketone; ester solvents such as ethyl acetate and butyl acetate; and aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and hexamethylphosphoric triamide.
- halogenated solvents such as methylene chloride and chloroform
- hydrocarbon solvents such as hexane, heptane,
- the solvent may be used alone or in combination thereof, if necessary.
- the acyloxylation may be carried out without a solvent, depending on the kind of an alkylating agent and/or base to be used.
- the solvent may be commercially available one.
- An amount of the solvent used in the acyloxylation is preferably from 0.0 g to 2,000.0 g, more preferably from 0.0 g to 500.0 g, per mol of 2-isopropenyl-5-methyl-4-hexen-1-ol in view of the economy.
- a reaction temperature in the acyloxylation is preferably from ⁇ 30° C. to 250° C., more preferably from 25° C. to 180° C., in view of the reactivity and yield.
- R 2 in the general formula (6) represents a linear or branched monovalent hydrocarbon group having 1 to 6, preferably 1 to 4 carbon atoms.
- R 2 is derived from the acylating agent used in the aforesaid (A), the carboxylic acid used in (B) or (D), and the carboxylate ester used in (C).
- Examples of the hydrocarbon group, R 2 include linear saturated hydrocarbon groups such as a methyl group, an ethyl group, a 1-propyl group, and a 1-butyl group; branched saturated hydrocarbon groups such as a 2-propyl group, a 2-methylpropyl group, a 2-butyl group, a 2-pentyl group, and a 1,1-dimethylethyl group; linear unsaturated hydrocarbon groups such as a 1-propenyl group, a 1-butenyl group, a 2-butenyl group, a 1-pentenyl group, and a 2-pentenyl group; and branched unsaturated hydrocarbon groups such as a 1-methylpropenyl group, a 2-methylpropenyl group, a 2-methylbutenyl group, and a 2-methyl-2-butenyl group.
- linear saturated hydrocarbon groups such as a methyl group, an ethyl group, a 1-propyl group, and a 1-butyl
- Examples of the 2-isopropenyl-5-methyl-4-hexen-1-yl carboxylate (6) include linear saturated carboxylate esters such as 2-isopropenyl-5-methyl-4-hexen-1-yl acetate, 2-isopropenyl-5-methyl-4-hexen-1-yl propionate, and 2-isopropenyl-5-methyl-4-hexen-1-yl butanoate; branched saturated carboxylate esters such as 2-isopropenyl-5-methyl-4-hexen-1-yl 2-methylpropionate, 2-isopropenyl-5-methyl-4-hexen-1-yl 2-methylbutanoate, 2-isopropenyl-5-methyl-4-hexen-1-yl 3-methylbutanoate, and 2-isopropenyl-5-methyl-4-hexen-1-yl 2,2-dimethylpropionate; linear unsaturated carboxylate esters such as 2-isopropenyl-5-methyl-4-hexen-1-y
- 2-isopropenyl-5-methyl-4-hexen-1-yl carboxylate (6) the following was identified as a sex pheromone component of mealybugs: 2-isopropenyl-5-methyl-4-hexen-1-yl 3-methyl-2-butenoate identified for vine mealybug (scientific name: Planococcus ficus ); 2-isopropenyl-5-methyl-4-hexen-1-yl acetate and 2-isopropenyl-5-methyl-4-hexen-1-yl propionate identified for banana mealybug (scientific name: Dysmicoccu grassii ); and 2-isopropenyl-5-methyl-4-hexen-1-yl 2-methylbutanoate identified for pink hibiscus mealybug (scientific name: Maconelhcoccus hirsutus ) and madeira mealybug (scientific name: Phenacoccus madeirensis ).
- the 2-isopropenyl-5-methyl-4-hexen-1-yl carboxylate (6) includes an enantiomer and a diastereomer thereof, and equimolar or non-equimolar mixtures thereof.
- 2-isopropenyl-5-methyl-4-hexenoic acid 2-isopropenyl-5-methyl-4-hexen-1-ol known as a perfume
- 2-isopropenyl-5-methyl-4-hexenyl carboxylates which are sex pheromone substances of mealybugs, are prepared industrially, conveniently, and economically.
- purity as used herein means an area percentage in gas chromatography (hereinafter referred to also as “GC”), unless otherwise specified.
- production ratio means a ratio of area percentages in GC.
- yield is calculated from the area percentages determined by GC.
- conversion is calculated from a sum of area percentages of raw materials and a target compound and an area percentage of the target compound, determined by GC.
- GC Capillary gas chromatograph GC-2010 (Shimadzu Corporation); column: DB-5, 0.25 mm ⁇ 0.25 mm ⁇ 30 m; carrier gas: He (1.55 mL/min), detector: FID; column temperature: held at 70° C. for 3 minutes, elevated in a rate of 10° C./min, and up to 250° C.
- GC Capillary gas chromatograph GC-2010 (Shimadzu Corporation); column: DB-WAX, 0.25 mm ⁇ 0.25 mm ⁇ 30 m; carrier gas: He (1.55 mL/min), detector: FID; column temperature: held at 120° C. for 12 minutes, elevated in a rate of 20° C./min, and up to 230° C.
- GC Capillary gas chromatograph GC-2010 (Shimadzu Corporation); column: DB-5, 0.25 mm ⁇ 0.25 mm ⁇ 30 m; carrier gas: He (1.55 mL/min), detector: FID; column temperature: held at 100° C. for 3 minutes, elevated in a rate of 10° C./min, and up to 250° C.
- 2-methyl-3-buten-2-ol (103.4 g: 1.2 mol) was added dropwise to the reaction mixture at a reaction mixture temperature of 65° C. to 70° C. over 1 hour. Then, the reaction mixture was stirred at a reaction mixture temperature of 68 to 70° C. for 8 hours. Then, the reaction mixture temperature was lowered to 55 to 60° C. Water (185.0 g) was then added to quench the reaction. Then, an aqueous phase was separated, and an organic phase was washed with an aqueous 5.0 wt % sodium hydroxide solution (250.0 g), and then with an aqueous 5.0 wt % sodium chloride solution (250.0 g).
- Infrared absorption spectrum (ATR method): ⁇ (cm ⁇ 1 ) 680, 776, 852, 921, 976, 1075, 1123, 1232, 1285, 1351, 1363, 1379, 1414, 1446, 1653, 1719, 2938, 1979, 3089.
- This crude product was purified by distillation at a reduced pressure to obtain t-butyl 2-isopropylidene-5-methyl-4-hexenoate (34.34 g, purity 94.2%).
- D-ATR Infrared absorption spectrum
- D-ATR Infrared absorption spectrum
- the temperature of the prepared Grignard reagent (1) was adjusted to 25° C., to which 1,1,1,3,3,3-hexamethyldisilazane (209.8 g: 1.30 mol) was added dropwise at a reaction mixture temperature of 25° C. to 30° C. over 2 hours. After the completion of the dropwise addition, the reaction mixture was stirred at a reaction mixture temperature of 30° C. for 2 hours.
- reaction mixture was heated to 40° C., and 2-methyl-3-buten-2-yl 3-methyl-2-butenoate (3) (168.2 g: 1.00 mol) was added dropwise at a reaction mixture temperature of 40° C. to 45° C. over 2 hours. After the completion of the dropwise addition, the reaction mixture was stirred at a reaction mixture temperature of 45° C. to 50° C. for 10 hours. The reaction mixture was cooled to 20° C., and then 13.0 wt % hydrochloric acid (720.0 g) was added to quench the reaction.
- the aqueous phase was separated, and an aqueous 12.0 wt % sodium hydroxide solution (382.0 g) and toluene (93.0 g) were placed to the organic phase, followed by phase separation to obtain the organic phase and the aqueous phase.
- the resulting aqueous phase was made acid by dropwise addition of 20.0 wt % hydrochloric acid (250.0 g).
- toluene (220.0 g) was added and subjected to extraction, and the aqueous phase was removed.
- the resulting organic phase was washed with an aqueous 6.5 wt % sodium chloride solution (268.0 g) twice.
- Infrared absorption spectrum (ATR method): ⁇ (cm ⁇ 1 ) 578, 744, 774, 899, 1110, 1207, 1251, 1288, 1378, 1413, 1440, 1647, 1707, 2917, 2973, 3081.
- the obtained 2-isopropenyl-5-methyl-4-hexenoic acid (4) was used as such, without being purified, in a subsequent step.
- the obtained 2-isopropenyl-5-methyl-4-hexenoic acid (4) was used as such, without being purified, in a subsequent step.
- Example 2 The procedures of Example 2 were repeated with the exception that phenyl chloride (135.1 g: 1.20 mol) was used instead of 2-hexyl chloride as an organohalide to obtain 2-isopropenyl-5-methyl-4-hexenoic acid (4) (154.7 g: 0.92 mol, yield 91.9%, purity 95.2%, conversion 95.1%).
- the obtained 2-isopropenyl-5-methyl-4-hexenoic acid (4) was used as such, without being purified, in a subsequent step.
- Example 2 The procedures of Example 2 were repeated with the exception that 1-propyl bromide (147.6 g: 1.20 mol) was used instead of 2-hexyl chloride as an organohalide to obtain 2-isopropenyl-5-methyl-4-hexenoic acid (4) (134.6 g: 0.80 mol, yield 80.0%, purity 89.8%, conversion 99.6%).
- the obtained 2-isopropenyl-5-methyl-4-hexenoic acid (4) was used as such, without being purified, in a subsequent step.
- Example 2 The procedures of Example 2 were repeated with the exception that 1-pentyl bromide (181.3 g: 1.20 mol) was used instead of 2-hexyl chloride as an organohalide to obtain 2-isopropenyl-5-methyl-4-hexenoic acid (4) (144.7 g: 0.86 mol, yield 86.0%, purity 91.2%, conversion 99.0%).
- the GC results of the obtained product showed that a regioisomer, 2-isopropylidene-5-methyl-4-hexenoic acid, was not formed.
- the obtained 2-isopropenyl-5-methyl-4-hexenoic acid (4) was used as such, without being purified, in a subsequent step.
- Infrared absorption spectrum (ATR method): ⁇ (cm ⁇ 1 ) 594, 720, 778, 838, 889, 1039, 1111, 1199, 1280, 1337, 1376, 1415, 1441, 1645, 1673, 1730, 2728, 2616, 1667, 3073, 3362.
- Example 7-1 A Process for Preparing 2-isopropenyl-5-methyl-4-hexen-1-yl methanesulfonate
- reaction mixture was stirred at a reaction mixture temperature of 20° C. to 25° C. for 2 hours. Then, water (200.0 g) was added to quench the reaction. The mixture was subjected to extraction with n-hexane (280.0 g), and the aqueous phase was separated. The organic phase was washed with an aqueous 1.3 wt % sodium bicarbonate solution (170.0 g), and then with an aqueous 5.0 wt % sodium chloride solution (175.0 g). The solvent was then removed at a reduced pressure to obtain 2-isopropenyl-5-methyl-4-hexen-1-yl methanesulfonate (228.9 g: 0.99 mol, yield 99.4%, purity 94.7%).
- Infrared absorption spectrum (ATR method): ⁇ (cm ⁇ 1 ) 850, 891, 1006, 1077, 1145, 1226, 1269, 1347, 1377, 1447, 1650, 1719, 2915, 2970.
- reaction mixture was stirred at a reaction mixture temperature of 10° C. to 25° C. for 3 hours.
- the reaction mixture temperature was lowered to 0° C. to 5° C., and water (650.0 g) was then added to quench the reaction.
- the aqueous phase was separated, and the organic phase was successively washed with 5.0 wt % hydrochloric acid (800.0 g), water (1000.0 g), and an aqueous 5.0 wt % sodium bicarbonate solution (1,000.0 g).
- Infrared absorption spectrum (ATR method): ⁇ (cm ⁇ 1 ) 606, 639, 893, 974, 1039, 1240, 1364, 1377, 1449, 1647, 1743, 2917, 2970, 3075.
- reaction mixture was stirred at a reaction mixture temperature of 5° C. to 10° C. for 3 hours.
- the reaction mixture temperature was lowered to 0° C. to 5° C., and water (340.0 g) was then added to quench the reaction.
- water 340.0 g was then added to quench the reaction.
- the aqueous phase was separated, and the organic phase was successively washed with 5.0 wt % hydrochloric acid (500.0 g), an aqueous 5.0 wt % sodium chloride solution (350.0 g), and an aqueous 5.0 wt % sodium bicarbonate solution (350.0 g).
- Infrared absorption spectrum (ATR method): ⁇ (cm ⁇ 1 ) 807, 839, 892, 962, 1020, 1084, 1183, 1272, 1348, 1378, 1451, 1647, 1740, 2917, 2971, 3074.
- Infrared absorption spectrum (ATR method): ⁇ (cm ⁇ 1 ) 753, 837, 892, 980, 1014, 1083, 1151, 1182, 1238, 1262, 1355, 1378, 1461, 1647, 1735, 2879, 2935, 2969, 3075.
- reaction mixture was stirred at a reaction mixture temperature of 25° C. for 1 hour. Then, the reaction mixture temperature was heated to 40° C., and 2-methyl-3-buten-2-yl 3-methyl-2-butenoate (3) (168.2 g: 1.00 mol) was added dropwise at a reaction mixture temperature of 40° C. to 45° C. over 2 hours. After the completion of the dropwise addition, the reaction mixture was stirred at a reaction mixture temperature of 45° C. to 50° C. for 6 hours. The reaction mixture temperature was lowered to 0° C. to 5° C., and an aqueous 10 wt % sodium hydroxide solution (286.0 g) was then added to quench the reaction.
- the aqueous phase was then separated. To the resulting aqueous phase was added dropwise 20.0 wt % hydrochloric acid (400.0 g) to make the aqueous phase acid. Then, the aqueous phase was subjected to extraction with diethylether (270.0 g). The extract was washed with water (200.0 g) and, then, an aqueous 7.5 wt % sodium chloride solution (200.0 g), and the solvent was then removed at a reduced pressure to obtain 2-isopropenyl-5-methyl-4-hexenoic acid (4) (134.6 g: 0.80 mol, yield 80.9%, purity 80.9%, conversion 98.8%).
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Abstract
Description
- [Patent Literature 1] Japanese Patent Application Laid-Open No. 2015-110553
- [Non-Patent Literature 1] Diane M. Hinkens et. al., Tetrahedron Letters 42 (2001) 1619-1621.
- [Non-Patent Literature 2] I. d. Dealfonso et. al., J. Agric. Food Chem. 2012, 60, 11959-11964.
- [Non-Patent Literature 3] A. Zhang et. al., Environ. Entmol. 34, 2005, 264-270.
- [Non-Patent Literature 4] H.-Y. Ho, J. Chem. Ecol., (2009) 35, 724-732.
- [Non-Patent Literature 5] M. Matsui et. al., Agr. Biol. Chem., 1968, 32, 1246-1249.
R1MgX (1)
wherein R1 represents a linear, branched, or aromatic monovalent hydrocarbon group having 1 to 8 carbon atoms, and X represents a chlorine atom, a bromine atom, or an iodine atom,
and 1,1,1,3,3,3-hexamethyldisilazane to a deprotonation reaction to form a 1,1,1,3,3,3-hexamethyldisilazane derivative; and
to a rearrangement reaction in the presence of the 1,1,1,3,3,3-hexamethyldisilazane derivative to form 2-isopropenyl-5-methyl-4-hexenoic acid (4).
the process comprising a step of reducing 2-isopropenyl-5-methyl-4-hexenoic acid (4) thus prepared to form 2-isopropenyl-5-methyl-4-hexen-1-ol (5).
wherein R2 represents a linear or branched monovalent hydrocarbon group having 1 to 6 carbon atoms,
the process comprising esterifying 2-isopropenyl-5-methyl-4-hexen-1-ol (5) thus prepared to form 2-isopropenyl-5-methyl-4-hexen-1-yl carboxylate (6).
Yield (%)={[(weight of a product obtained by a reaction×% GC)/molecular weight of a product]÷[(weight of a starting material in a reaction×% GC)/molecular weight of a starting material]}×100
Claims (3)
R1MgX (1)
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US20150119598A1 (en) * | 2013-10-30 | 2015-04-30 | Shin-Etsu Chemical Co., Ltd. | Method for producing (e)-2-isopropyl-5-methyl-2,4-hexadienyl acetate |
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